Microwave irradiation (MI) was applied to the atom transfer radical bulk polymerization of methyl methacrylate. The influence of the amount of the refluxing solvent used for controlling the polymerization temperature, irradiation power, irradiation time, and initiator concentration on the conversion, molecular weight, and molecular weight distribution of the polymers was studied with a benzyl chloride/cuprous chloride/2,2'-bipyridyl initiation system and compared with the corresponding conventional heating (CH) process. In comparison with CH, the results can be summarized as follows. The polymerization rate for reaching 70% conversion increased 2.6-5.1 times under an irradiation power of 270-630 W. The apparent increasing rate constant was much larger than that with CH and increased with the irradiation power. MI produced a higher polymerization rate and conversion even if the concentration of the initiation system was very low (initial monomer concentration/initial initiator concentration=200:0.33 mol/mol) and the polydispersity index (DI) was narrower; however, CH yielded almost no polymers. MI promoted the activities of the catalyst and monomer, and its initiation efficiency was higher than that with CH and increased with the irradiation power. MI obviously played an important role in promoting the polymerization rate of atom transfer radical polymerization (ATRP). MI reduced the concentration of the initiation system and perhaps made ATRP controlled (cf. uncontrolled ATRP with CH); at the same time, it made the DI values of the polymers narrower. In comparison with the initiation efficiencies found with benzyl bromide and 2,2'-azobisisobutyronitrile used as initiators, the initiation efficiency with p-toluene sulfonyl chloride used as an initiator was higher; moreover, DI was much narrower (1.17), and the polymerization rate was greater. (C) 2003 Wiley Periodicals, Inc.
